European Journal of Organic Chemistry

Cover image for Vol. 2015 Issue 34

Early View (Online Version of Record published before inclusion in an issue)

Editor: Haymo Ross, Deputy Editor: Susan Wilkinson

Impact Factor: 3.065

ISI Journal Citation Reports © Ranking: 2014: 14/58 (Chemistry Organic)

Online ISSN: 1099-0690

Associated Title(s): Advanced Synthesis & Catalysis, Asian Journal of Organic Chemistry


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  1. Short Communications

    1. Subphthalocyanines

      Acetylenic Scaffolding with Subphthalocyanines

      Henrik Gotfredsen, Martyn Jevric, Anders Kadziola and Mogens Brøndsted Nielsen

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501264

      Thumbnail image of graphical abstract

      A boron subphthalocyanine with a terminal alkyne unit at the axial position was prepared and subjected to a variety of metal-catalyzed cross-coupling reactions.

  2. Full Papers

    1. Steroids

      Total Synthesis of (–)-C/D-cis-De­hydro-3-O-methyl-estradiols

      Nora M. Kaluza, Dieter Schollmeyer and Udo Nubbemeyer

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501341

      Thumbnail image of graphical abstract

      Optically active iodolactones served as starting materials for the total synthesis of steroid derivatives. A starting sequence involving an intramolecular Grignard acylation delivered a key tetralone. Generation of the C-ring involved a ring-closing metathesis reaction. Finally, reductive cyclisation with samarium diiodide diastereoselectively delivered estradiol derivatives with a C/D-cis ring junction.

    2. Organocatalysis

      Proline Sulfonamide-Catalyzed, ­Domino Process for Asymmetric Synthesis of Amino- and Hydroxy-Substituted Bicyclo[2.2.2]octanes

      Mohamed F. El-Mansy, Jun Yong Kang, Rajinikanth Lingampally and Rich G. Carter

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501302

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      A generalized method for accessing highly functionalized NH2- and OH-substituted bicyclo[2.2.2]octanes via p-dodecylphenylsulfonamide catalyst in a good enantio- and diasteroselective fashion has been developed. A discussion of the mechanistic underpinnings of this transformation is presented.

    3. Glycal Chemistry

      Sulfonium Salts of Iodine(I) Species as Efficient Reagents for the Regioselective Bisfunctionalisation of ­Glycals and Enol Ethers

      Thurpu Raghavender Reddy, Dodla Sivanageswara Rao, Kalvacherla Babachary and Sudhir Kashyap

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501183

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      A new sulfonium-salt-based iodine(I) reagent system has been developed for the vicinal functionalisation of glycals and enol ethers. The unprecedented iodine(I) complex generated in situ from Me3SI and PhI(OAc)2 effectively promoted iodocarboxylation and iodoazidation reactions in excellent yields and with diastereoselectivities up to 100 %.

    4. Deamidation Coupling

      Practical Synthesis of Phenanthrid­inones by Palladium-Catalyzed One-Pot C–C and C–N Coupling Reaction: Extending the Substrate Scope to o-Chlorobenzamides

      Hailong Liu, Weibiao Han, Chun Li, Zhiyong Ma, Ruixiang Li, Xueli Zheng, Haiyan Fu and Hua Chen

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501170

      Thumbnail image of graphical abstract

      A highly efficient palladium-catalyzed phosphine-free domino reaction for the construction of phenanthridinone derivatives using o-halobenzamides has been developed. This protocol exhibits broad substrate scope, and a series of phenanthridinones derivatives were obtained with high yields. Importantly, this reaction system could also be applied for the less reactive and less expensive o-chlorobenzamides.

    5. Synthesis of Thiosaponins

      Synthesis and Cytotoxicity of 28a-Homothiolupanes and 28a-Homothiolupane Saponins

      Katarzyna Sidoryk, Anna Korda, Lucie Rárová, Jana Oklešťková, Zbigniew Pakulski, Miroslav Strnad, Piotr Cmoch, Katarzyna Gwardiak and Romuald Karczewski

      Article first published online: 25 NOV 2015 | DOI: 10.1002/ejoc.201501147

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      Homothiolupane-type triterpenes have been synthesized by elongation of the carbon chain followed by nucleophilic substitution with thiocyanate ion. The corresponding saponins were obtained by glycosylation of homothiobetulin. Cytotoxic activities were evaluated in vitro. The influence of the allyl protecting group on the cytotoxicity is discussed.

  3. Short Communications

    1. C–C Bond Formation

      Tandem C–C Bond Cleavage of ­Cyclopropanols and Oxidative Aromatization by Manganese(IV) Oxide in a Direct C–H to C–C Functionalization of Heteroaromatics

      Desta Doro Bume, Cody Ross Pitts and Thomas Lectka

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501405

      Thumbnail image of graphical abstract

      Manganese(IV) oxide plays a dual role in this C–C bond-forming reaction involving cyclopropanols and heteroaromatics. A diverse substrate scope and good yields are highlighted, as well as potential applications to natural product synthesis, complex molecule derivatization, and preliminary mechanistic investigations.

  4. Full Papers

    1. C–H Functionalization

      Regioselective Coupling Reactions of Coumarins with Aldehydes or Di-tert-butyl Peroxide (DTBP) through a C(sp2)–H Functionalization Process

      Wannian Zhao, Lei Xu, Yingcai Ding, Ben Niu, Ping Xie, Zhaogang Bian, Denghong Zhang and Aihua Zhou

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501251

      Thumbnail image of graphical abstract

      Two coupling reactions that regioselectively yield either keto- or methyl-substituted coumarin derivatives by proceeding through a C(sp2)–H functionalization process were successfully developed. The coupling of coumarins with either aldehydes or di-tert-butyl peroxide (DTBP) generated the corresponding products in moderate to good yields.

    2. Pyridyl–Oxazole Oligomers

      Linear and Branched Pyridyl–Oxazole Oligomers: Synthesis and Circular Dichroism Detectable Effect on c-Myc G-Quadruplex Helicity

      Natalia Rizeq and Savvas N. Georgiades

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501269

      Thumbnail image of graphical abstract

      A family of pyridyl–oxazole oligomers with either linear or branched connectivity of their subunits is synthesized. According to circular dichroism spectroscopy, some of the members of this family enhance the helicity of a partially folded c-myc G-quadruplex.

  5. Short Communications

    1. 1,3-Diol Synthesis

      A Chiral Building Block for the ­Stereocontrolled Installation of the 1,3-Diol Motif

      Angela Bredenkamp, Zhi-Bin Zhu and Stefan F. Kirsch

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501325

      Thumbnail image of graphical abstract

      A new chiral building block for the direct installation of the 1,3-diol motif is presented. Aldehyde olefination followed by directed reduction allows for the synthesis of both the syn- and the anti-configured diol in a fully stereocontrolled way.

  6. Full Papers

    1. Amino Acids

      Synthesis of Deuterium-Labelled 3-Hydroxy-L-arginine: Comparative Studies on Different Protecting-Group Strategies

      Anke Lemke and Christian Ducho

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501109

      Thumbnail image of graphical abstract

      This study on the synthesis of 3-hydroxy-L-arginine provides detailed insights into the development of the protecting-group strategy. This strategy was essential to allow a robust and reliable synthesis of the target amino acid. The optimized route was applied to the preparation of a deuterium-labelled congener for biosynthetic studies.

    2. Reactivity of Aryllithiums

      A Computational Study of the Intramolec­ular Carbolithiation of Aryllithiums: Solvent and Substituent Effects

      Jean-Marc Mattalia and Paola Nava

      Article first published online: 24 NOV 2015 | DOI: 10.1002/ejoc.201501208

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      This DFT study of the intramolecular carbolithiation of aryllithiums provides new insights into solvent and structural effects. Various computed structures are in good agreement with literature data.

  7. Short Communications

    1. Synthetic Methods

      Synthesis of Functionalized Ring C of Escobarines

      Harim Lechuga-Eduardo, Moises Romero-Ortega and Horacio F. Olivo

      Article first published online: 23 NOV 2015 | DOI: 10.1002/ejoc.201501312

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      A hydroxymethyl group was introduced into C3 of cyclohexenone applying the umpolung concept. (Hydroxymethyl)cyclohexenone was properly functionalized to provide α-acetylene-α,β-epoxy-β-formyl and α-acetylene-α,β-epoxy-β-(hydroxymethyl)cyclohexanone as a model study for a proposed syntheses of escobarines A and B.

    2. P-Stereogenic N-Phosphinyl Compounds

      Stereoselective Synthesis of P-Stereogenic N-Phosphinyl Compounds

      Ahmed Chelouan, Rocío Recio, Eleuterio Álvarez, Noureddine Khiar and Inmaculada Fernández

      Article first published online: 23 NOV 2015 | DOI: 10.1002/ejoc.201501260

      Thumbnail image of graphical abstract

      A number of P-stereogenic N-phosphinyl compounds are stereoselectively prepared by a straightforward approach, thanks to the diversified and, up until now, unexplored reactivity of (R)- and (S)-dicyclohexylidene-D-glucose methyl phenyl phosphinates toward metal amides. Under adequate conditions, structurally different phosphinamides with one or two P-chiral centers are obtained.

  8. Full Papers

    1. Terpyridine Derivatives

      Functionalization of Highly Substituted 2,2′:6′,2″-Terpyridine Derivatives

      Paul Hommes and Hans-Ulrich Reissig

      Article first published online: 23 NOV 2015 | DOI: 10.1002/ejoc.201501299

      Thumbnail image of graphical abstract

      Diversity is good! By appropriate functionalization, a variety of new 2,2′:6′,2″-terpyridine derivatives is accessed. Key is the formation of N-oxides, followed by Boekelheide rearrangement, which allows the preparation of bis(acetoxymethyl)-substituted compounds.

    2. Spiroketal Natural Products

      Synthesis of the Spiroketal Core of the Pinnatifinoside Family of Natural Products

      Daniel F. Chorley, Daniel P. Furkert and Margaret A. Brimble

      Article first published online: 23 NOV 2015 | DOI: 10.1002/ejoc.201501225

      Thumbnail image of graphical abstract

      The successful synthesis of the spiroketal core of the pinnatifinoside family of natural products has been undertaken. Sonagashira cross-coupling and gold-catalyzed spirocyclization of functionalised flavones enabled access to the key ring system. This work lays the platform for ongoing synthetic studies towards the total syntheses of members of the natural product family and their biologically active derivatives.

  9. Short Communications

    1. Total Synthesis

      Total Synthesis of the Proposed Structure of Turkiyenine

      Hisataka Kobayashi, Yusuke Sasano, Naoki Kanoh, Eunsang Kwon and Yoshiharu Iwabuchi

      Article first published online: 20 NOV 2015 | DOI: 10.1002/ejoc.201501365

      Thumbnail image of graphical abstract

      The total synthesis of the proposed structure of turkiyenine is reported. The route features an aza-spiroannulation onto a benzofuran via a rhodium–nitrenoid to construct a 3-alkyl-3-amino-2,3-dihydrobenzofuran, an acyl-alkylation of an aryne with a β-ketolactam to form a 3-benzazepine-1-one, and a chemoselective reduction of an amide in the presence of a ketone as key steps. Significantly, our synthetic work calls for a structural revision of turkiyenine.

  10. Full Papers

    1. Oxidative C–H Functionalization

      Hypervalent Iodine Promoted Regioselective Oxidative C–H Functionalization: Synthesis of N-(Pyridin-2-yl)benzo[d]thi­azol-2-amines

      Arumugam Mariappan, Kandasamy Rajaguru, Somi Santharam Roja, Shanmugam Muthusubramanian and Nattamai Bhuvanesh

      Article first published online: 20 NOV 2015 | DOI: 10.1002/ejoc.201501202

      Thumbnail image of graphical abstract

      Biologically potent N-(pyridin-2-yl)benzo[d]thiazol-2-amines were conveniently synthesized from simple heteroaryl-thioureas through an oxidative C–S bond formation strategy that employed phenyliodine(III) bis(trifluoroacetate) as the oxidant.

    2. O- vs. C-Alkylation

      Synthesis of 5-Phosphonoisoxazol­ine N-Oxides by Selective O-Alkylation of Nitronate Anions

      Vincent Perez, Nicolas Rabasso and Antoine Fadel

      Article first published online: 20 NOV 2015 | DOI: 10.1002/ejoc.201501243

      Thumbnail image of graphical abstract

      5-Phosphonoisoxazoline N-oxides are prepared in good to excellent yields by selective O-alkylation of nitronate anions with (α-tosyloxyvinyl)phosphonates. A comprehensive study is undertaken to limit the competitive formation of the (β-nitrocyclopropyl)phosphonate resulting from C-alkylation of the ambident nitronate anions. Ts = para-tolylsulfonyl, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene.

    3. Oxidative Coupling

      Solvent and Temperature Effects on the Platinum-Catalyzed Oxidative Coupling of 1-Naphthols

      Mabuatsela V. Maphoru, Josef Heveling and Sreejarani Kesavan Pillai

      Article first published online: 20 NOV 2015 | DOI: 10.1002/ejoc.201501280

      Thumbnail image of graphical abstract

      1-Naphthols with electron-donating groups at the 2- and 4-positions couple oxidatively over platinum to 3,3′-substituted 1,1′-binaphthalenylidene-4,4′-diones and the 4,4′-substituted 2,2′-binaphthalenylidene-1,1′-diones, respectively. The binaphthalenyl diols are the intermediates. Oxidation to naphthoquinones competes with the coupling reaction.

  11. Short Communications

    1. Multicomponent Reactions

      Ring-Opening of Pyridines with Acyl­acetylenes and Water: Straightforward Access to 5-[(Z)-Acylethenyl]amino-2,4-pentadienals

      Boris A. Trofimov, Ludmila V. Andriyankova, Kseniya V. Belyaeva, Lina P. Nikitina, Andrei V. Afonin and Anastasiya G. Mal'kina

      Article first published online: 19 NOV 2015 | DOI: 10.1002/ejoc.201501286

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      Pyridines undergo exceptionally facile ring opening under the action of acylacetylenes and water to afford 5-[(Z)-acylethenyl]amino-2,4-pentadienals in 84–92 % yield. The reaction is stereoselective, as only the Z configuration is observed for ethenyl substituents and preferentially the E,E configuration (in addition to the E,Z configuration) for the 2,4-pentadienal moiety.

  12. Full Papers

    1. Selective Sulfenylation

      Regioselective Mono- and Bis-Sulfenylation of Active Methylene Compounds

      Namita Devi, Rajjakfur Rahaman, Kuladip Sarma and Pranjit Barman

      Article first published online: 18 NOV 2015 | DOI: 10.1002/ejoc.201501148

      Thumbnail image of graphical abstract

      Selective mono- and bis-sulfenylation of active methylene groups with disulfides at ambient temperature is reported. Sulfenylation is promoted by iodine as catalyst and sulfenyl iodides as intermediates, under metal-free conditions. The method is greener in terms of solvent selection and the use of DMSO as an oxidant. The procedure is highly efficient, with good to excellent yields.

  13. Short Communications

    1. Organophotocatalysis

      Benign Perfluoroalkylation of Aniline Derivatives through Photoredox Organocatalysis under Visible-Light Irradiation

      Sebastián Barata-Vallejo, Damian E. Yerien and Al Postigo

      Article first published online: 18 NOV 2015 | DOI: 10.1002/ejoc.201501189

      Thumbnail image of graphical abstract

      We have developed a photocatalytic CAr–Rf bond formation reaction by homolytic aromatic substitution (HAS) with an inexpensive organic dye, Rose Bengal, in the absence of transition metals, through irradiation at ambient temperature with visible light by using readily available perfluoroalkyl halides. This method was applied to the synthesis of a variety of perfluoroalkyl-substituted aniline derivatives.

  14. Full Papers

    1. Nucleobase Analogues

      Modification of Pyrrolo[2,3-d]pyrimidines by C–H Borylation Followed by Cross-Coupling or Other Transformations: Synthesis of 6,8-Disubstituted 7-Deazapurine Bases

      Martin Klečka, Lenka Poštová Slavětínská and Michal Hocek

      Article first published online: 17 NOV 2015 | DOI: 10.1002/ejoc.201501177

      Thumbnail image of graphical abstract

      Substituted 7-deazapurine nucleobase analogues were prepared by C–H borylation, Suzuki coupling and further functional group transformations.

    2. Free-Radical Nitration

      Nitropyrene Photoprobes: Making Them, and What Are They Good for?

      Eli M. Espinoza, Bing Xia, Narek Darabedian, Jillian M. Larsen, Vicente Nuñez, Duoduo Bao, Jenny T. Mac, Fabian Botero, Michelle Wurch, Feimeng Zhou and Valentine I. Vullev

      Article first published online: 17 NOV 2015 | DOI: 10.1002/ejoc.201501339

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      Employing NO2/N2O4 nitration mixture on esters of pyrenecarboxylic acid provides routes toward a diverse set of nitropyrene derivatives. The nitro groups have dominating effect on the electrochemical and photophysical properties of these disubstituted pyrenes.

    3. Heterocyclic Chemistry

      Investigation of a Late-Stage Derivatiza­tion Approach to Isatogens: Discovery of New Reaction Pathways

      Steven J. Edeson, Elvis J. M. Maduli, Stephen Swanson, Panayiotis A. Procopiou and Joseph P. A. Harrity

      Article first published online: 17 NOV 2015 | DOI: 10.1002/ejoc.201501372

      Thumbnail image of graphical abstract

      Take your pick. 2-Iodoisatogens represent readily accessible precursors to a range of 3-oxindole products. Specifically, 2-aryl- and 2-alkyl-isatogens, as well as N-alkoxy 2,2-disubstituted 3-oxindoles and angularly fused heterocycles can all be prepared by judicious choice of a Zn-based organometallic reagent.

    4. α-Amino Phosphonates

      Convenient Synthesis of Cyclic α-Aminophosphonates by Alkylation–Cyclization Reaction of Iminophosphoglycinates Using Phase-Transfer Catalysis

      Oscar Abelardo Ramírez-Marroquín, Iván Romero-Estudillo, José Luis Viveros-Ceballos, Carlos Cativiela and Mario Ordóñez

      Article first published online: 17 NOV 2015 | DOI: 10.1002/ejoc.201501203

      Thumbnail image of graphical abstract

      The alkylation reaction of diethyl N-(diphenylmethylene)aminomethylphosphonate with alkyl dihalides under phase-transfer catalysis followed by hydrolysis of the imine functionality and subsequent cyclization provides a simple and convenient method for the synthesis of known and new cyclic α-amino phosphonates in moderate to good yields.

    5. C-Nucleosides

      Synthesis of Benzene and Pyridine 2′-C-Methyl-C-ribonucleosides and -nucleotides

      Anna Tokarenko, Lenka Poštová Slavětínská, Blanka Klepetářová and Michal Hocek

      Article first published online: 17 NOV 2015 | DOI: 10.1002/ejoc.201501219

      Thumbnail image of graphical abstract

      C-Nucleoside carba-analogues of clinically used antiviral 2′-C-methylribonucleosides were designed and synthesized, but were found to be inactive.

    6. Fluorinatd Molecules

      Palladium-Catalysed Synthesis of α-(Trifluoromethyl)styrenes by Means of Directed C–H Bond Functionalization

      Qun Zhao, Tatiana Besset, Thomas Poisson, Jean-Philippe Bouillon and Xavier Pannecoucke

      Article first published online: 16 NOV 2015 | DOI: 10.1002/ejoc.201501217

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      The first introduction of 2-bromo-3,3,3-trifluoropropene (BTP) by directed C–H bond functionalization is described. The products were obtained in good yields, and the method represents a straightforward route to α-(trifluoromethyl)styrenes.

    7. Heterocycles

      Domino Oxidative Cyclization of 2-Amino­acetophenones for the One-Pot Synthesis of Tryptanthrin Derivatives

      B. V. Subba Reddy, D. Maheswara Reddy, G. Niranjan Reddy, M. Ramana Reddy and V. Krishna Reddy

      Article first published online: 16 NOV 2015 | DOI: 10.1002/ejoc.201501079

      Thumbnail image of graphical abstract

      A new DMSO/CuI-catalysed oxidative domino process has been developed for the one-pot synthesis of tryptanthrin derivatives.

    8. Oligoaryls*

      Atropisomerism of 2,2′-Diaryl-1,1′-binaphthalenes Containing Three Stereo­genic Axes: Experimental and Computational Study

      Marcel Ehn, Nikolay Georgiev Vassilev, Lukáš Félix Pašteka, Miroslav Dangalov and Martin Putala

      Article first published online: 16 NOV 2015 | DOI: 10.1002/ejoc.201500840

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      Atropisomerization barriers in sets of three diastereomeric atropisomers were determined by dynamic 2D NMR and compared with theoretical values. Use of single-point calculations based on the B2-PLYP functional improved prediction of relative enthalpy values. The binaphthalene moiety assists in lowering the rotational barrier for the most congested bis(isopropylphenyl) derivative.

  15. Short Communications

    1. [4+3] Cycloaddition

      Rhodium-Catalyzed [4+3] Cycloaddition to Furans: Direct Access to Functionalized Bicyclo[5.3.0]decane Derivatives

      Tanja Krainz, Sharon Chow, Natasa Korica, Paul V. Bernhardt, Glen M. Boyle, Peter G. Parsons, Huw M. L. Davies and Craig M. Williams

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501271

      Thumbnail image of graphical abstract

      A cyclic donor–acceptor diazo compound was synthesized for the first time, facilitating direct access to the bicyclo[5.3.0]decane motif, which is commonly seen in a number of prominent natural products active against cancer. Some examples were evaluated against various PKC cancer cell lines.

  16. Full Papers

    1. syn- and anti-Selective Aldol Additions

      Aldol Additions of Titanium and Boron Enolates of Achiral and Chiral δ-Lactones to Achiral Model Aldehydes: Simple and Induced Diastereoselectivities

      Fabian Weber, Fabian Becker, Manfred Keller, Harald Hillebrecht and Reinhard Brückner

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501128

      Thumbnail image of graphical abstract

      Aldol additions of CpTiCl2 and Bu2B enolates of δ-lactone and its monomethyl derivatives to model aldehydes were studied. The CpTiCl2 enolates reacted syn-selectively (ds >95:5), the Bu2B enolates anti-selectively (ds up to 98:2). The α-hydroxyalkyl groups were oriented trans relative to the lactone's β- or γ-methyl group but cis relative to the lactone's δ-methyl group.

    2. Radiosynthesis – Homoharringtonine

      Total Synthesis of [14C]-Labelled Homoharringtonine

      Melanie Marguerit, Gill Little, Yi Wang, Linli He, Shawn Allwein, James Reif, Jason Rossi, Renee Roemmele and Roger Bakale

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201500906

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      The total synthesis of (–)-[14C]homoharringtonine, for use in clinical studies, was achieved 17-steps, starting from 14C-labelled potassium cyanide.

    3. Click Chemistry

      BEt3-Initiated Thiol–Ene Click Reactions as a Versatile Tool To Modify Sensitive Substrates

      Jan Gorges and Uli Kazmaier

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201500915

      Thumbnail image of graphical abstract

      BEt3-initiated thiol–ene click reactions proceed under very mild conditions, and require only 10 mol-% of BEt3 and an almost stoichiometric amount of thiol. The mild reaction conditions allow the modification of substrates containing functionalities that are senstitive to H-abstraction.

    4. Sulfur–Nitrogen Heterocycles

      Palladium-Catalyzed Regio- and Chemo­selective Reactions of 2-Bromobenzyl Bromides: Expanding the Scope for the Synthesis of Biaryls Fused to a Seven-Membered Sultam

      Joydev K. Laha, Shubhra Sharma and Neetu Dayal

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501032

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      A palladium-catalyzed domino reaction of N-alkylbenzenesulfonamides and 2-bromobenzyl bromides gives biaryls fused to a seven-membered sultam. This approach employs readily accessible substrates and provides speedy access to fused-ring compounds.

    5. 1,3-Diene Derivatives

      Base-Promoted Approach to Highly Functionalized Conjugated Dienes through Enamine Migration

      Yulei Zhao, Fangfang Zhang, Wenjun Yao, Chengyu Wang, Yuanyuan Liu and Yanzhong Li

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501060

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      An efficient and chemoselective nitrogen nucleophilic addition/enamine migration cascade reaction is described, in which a broad range of enaminones and propynyl carbonyl compounds are converted into 1,3-diene derivatives in good to high yields. The reaction mechanism is investigated by cross-reaction experiments.

    6. Indium Chemistry

      Ohmic Heating and Ionic Liquids in Combination for the Indium-Promoted Synthesis of 1-Halo Alkenyl Compounds: Applications to Pd-Catalysed Cross-Coupling Reactions

      Raquel G. Soengas, Vera L. M. Silva, Joana Pinto, Humberto Rodríguez-Solla and Artur M. S. Silva

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501162

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      We report herein the combination of ohmic heating (ΩH) with ionic liquids for the indium-promoted dehalogenation of gem-dibromo alkenes and the indium-mediated reductive elimination of chlorohydrins. The 1-halo alkenyl derivatives synthesized were then submitted to a series of cross-coupling reactions to give conjugated alkenes, dienes and enynes.

    7. Benzyl Esters

      O-Benzylation of Carboxylic Acids Using 2,4,6-Tris(benzyloxy)-1,3,5-triazine (TriBOT) under Acidic or Thermal Conditions

      Kohei Yamada, Saki Yoshida, Hikaru Fujita, Masanori Kitamura and Munetaka Kunishima

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501172

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      Two methods for the O-benzylation of carboxylic acids using TriBOT have been developed under either acidic or thermal conditions. The O-benzylation of hydroxy carboxylic acids afforded the dibenzylated product under acidic conditions and the hydroxy ester under thermal conditions. The former reaction proceeds through an SN1-type mechanism and the latter by an SN2-type mechanism.

    8. [3,3]-Sigmatropic Rearrangement

      Triflimide-Catalysed Rearrangement of N-(1-Trimethylsilyl)allylhydrazones Results in the Formation of Vinylsilanes and Cyclopropanes

      Sebastian Dittrich and Franz Bracher

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501180

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      Triflimide-mediated rearrangement of N-(1-trimethylsilyl)allylhydrazones gives terminal vinylsilanes through a “traceless bond construction”. A side-reaction resulting in the formation of cyclopropanes from aromatic hydrazones is described.

    9. C–H Acylation

      Palladium-Catalyzed Oxidative Direct ortho-C–H Acylation of Arenes with Aldehydes under Aqueous Conditions

      Fuhong Xiao, Shuqing Chen, Huawen Huang and Guo-Jun Deng

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501187

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      Palladium-catalyzed ortho-acylation with aldehydes in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under aqueous conditions has been demonstrated. The acylation reaction exhibits excellent regioselectivity and wide functional group tolerance.

    10. Natural Product Synthesis

      Synthetic Studies towards Communesins: Diastereoselective Oxidative Rearrangement of Aurantioclavine Derivatives

      Satoshi Suetsugu, Chihiro Tsukano and Yoshiji Takemoto

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501194

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      The pentacyclic skeleton of the communesins has been prepared by the oxidative rearrangement of aurantioclavine derivatives, which are believed to be biosynthetic intermediates of the communesin alkaloids. The quaternary C-7 carbon center was constructed in a stereoselective manner, and the isolation of a 2-ethoxyindolenine intermediate was critical to the success of the strategy.

    11. Asymmetric Catalysis

      Enantioselective Construction of the Biologically Important Cyclopenta[1,4]diazepine Framework Enabled by Asymmetric Catalysis by Chiral Spiro-Phosphoric Acid

      Meng Sun, Yang Wang, Lei Yin, Yang-Yan Cao and Feng Shi

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501255

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      A chiral spiro-phosphoric-acid-catalyzed asymmetric approach for constructing the biologically important cyclopenta[1,4]diazepine scaffold with high enantioselectivity (up to 98:2 er) has been established through the use of three-component tandem reactions of cyclopentane-1,3-dione, 1,2-phenylenediamine, and isatins under mild reaction conditions.

  17. Short Communications

    1. Calcium Catalysis

      Calcium-Catalyzed Synthesis of 1,2-Disubstituted 3-Benzazepines

      Helena Damsen and Meike Niggemann

      Article first published online: 13 NOV 2015 | DOI: 10.1002/ejoc.201501106

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      A new stereoselective chiral pool synthesis of 1,2-disubstituted 3-benzazepines was developed, using enantiopure amino acids as chiral building blocks. The key step is based on the first diastereoselective Friedel–Crafts cyclization towards this pharmacologically highly interesting compound class and accomplished by a biocompatible calcium catalyst. The modular concept allows for variation of all substituents, leaving the general synthetic route unchanged.

  18. Microreviews

    1. C–H Functionalization

      Recent Advances in First-Row-Transition-Metal-Catalyzed Dehydrogenative Cou­pling of C(sp3)–H Bonds

      Jinmin Miao and Haibo Ge

      Article first published online: 11 NOV 2015 | DOI: 10.1002/ejoc.201501186

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      In this review, we discuss recent progress in two classes of first-row transition-metal-catalyzed dehydrogenative reaction of C(sp3)–H bonds: (1) intramolecular cyclizations for C–C bond formation, and (2) directed site-selective C–H functionalizations.

  19. Full Papers

    1. Nitroso-Based Fluorescence Probe

      Fast-Responsive Nitroso-Based Turn-On Probe for Hydrogen Sulfide

      Kévin Renault, Cyrille Sabot and Pierre-Yves Renard

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejoc.201501140

      Thumbnail image of graphical abstract

      Very few different reducible chemical functionalities have been used in the design of reduction-based fluorescent probes. Reported herein is a nitroso-based fluorescence turn-on probe that displays an almost instantaneous and strong fluorescence response towards hydrogen sulfide.

  20. Short Communications

    1. Squarimide Formation

      Unexpected Squaramide-Induced Cleavage of Benzils: Synthesis and Characterization of Mono-Aroyl Squarimides

      Elena Sanna, Carlos López, Pablo Ballester, Carmen Rotger and Antoni Costa

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejoc.201501235

      Thumbnail image of graphical abstract

      The facile preparation of mono-aroyl squarimide compounds is described. The reaction proceeds from the direct reaction of 4,4′-substituted benzils with squaramide compounds.

  21. Full Papers

    1. Intense CPL

      Highly Emissive Optically Active Conjugated Dimers Consisting of a Planar Chiral [2.2]Paracyclophane Showing Circularly Polarized Luminescence

      Masayuki Gon, Yasuhiro Morisaki and Yoshiki Chujo

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejoc.201501181

      Thumbnail image of graphical abstract

      Optically active X-shaped dimers based on the planar chiral [2.2]paracyclophane have been synthesized. The naphthalene-containing dimer exhibits an intense circularly polarized luminescence (CPL) signal with a high dissymmetry factor in the order of 10–3 in addition to a high ϵ and good photoluminescence quantum efficiency, which indicates that this compound is a highly emissive CPL material.

    2. Synthetic Methods

      Base-Induced One-Pot Preparation of N- or P-Substituted Alkynes

      Yang Zhang, Yanqin Zhang, Jing Xiao, Zhihong Peng, Wanrong Dong and Delie An

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejoc.201501092

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      An efficient method for the formation of C(sp)–N or C(sp)–P bonds is described. The facile transformation proceeds in the absence of any transition-metal catalysts under mild conditions (0 or –20 °C) in a one-pot manner with good functional group compatibility and with high efficiency.

    3. Nucleobase Derivatives

      5-Triazolyluracils and Their N1-Sulfonyl Derivatives: Intriguing Reactivity Differences in the Sulfonation of Triazole N1′-Substituted and N1′-Unsubstituted Uracil Molecules

      Dijana Saftić, Robert Vianello and Biserka Žinić

      Article first published online: 10 NOV 2015 | DOI: 10.1002/ejoc.201501088

      Thumbnail image of graphical abstract

      The synthesis of C5-triazolyl-substituted pyrimidines and C5-triazolyl derived N1-sulfonylpyrimidines is described. Computational studies of the sulfonation step shed light on the differences in reactivity and revealed a connection between the strength of the employed base and its tendency to increase the nucleophilicity of the reacting uracil N1 atom by deprotonation.

    4. Natural Product Synthesis

      Diastereoselective Synthesis of the A-B-C Tricyclic Ring Structure of Stemocurtisine

      Xuan Duc Dau, Anthony C. Willis and Stephen G. Pyne

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501080

      Thumbnail image of graphical abstract

      The diastereoselective synthesis of the A-B-C tricyclic ring structure of the Stemona alkaloid stemocurtisine has been developed. This tricyclic precursor to the natural product was obtained in 19 steps from a known vinyl iodide (TBS = tert-butyldimethylsilyl).

    5. Intramolecular O-Arylation

      Copper-Catalyzed Double Intramolecular Ullmann Coupling for the Synthesis of Diastereomerically and Enantiomerically Pure 4b,9b-Dihydrobenzofuro[3,2-b]benzofurans

      Hans-Georg Imrich, Jürgen Conrad and Uwe Beifuss

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501132

      Thumbnail image of graphical abstract

      Intramolecular double O-arylation of syn-1,2-bis(2-bromoaryl)ethane-1,2-diols delivers 4b,9b-dihydrobenzofuro[3,2-b]benzofurans in diastereomerically and enantiomerically pure form and yields of up to 90 %. The reaction can be carried out in aqueous acetonitrile with K3PO4 as the base, CuII oxinate as the catalyst, and KI as a reductant.

  22. Microreviews

    1. Carbohydrate Analogues

      Recent Developments in the Synthesis of 2-C-Branched and 1,2-Annulated Carbohydrates

      Yashwant D. Vankar and Torsten Linker

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501176

      Thumbnail image of graphical abstract

      This microreview highlights the recent developments in the synthesis of 2-C-branched and 1,2-annulated carbohydrates 2 and 3, respectively, during the last four years. The transformations proceed with high regio- and stereoselectivities, and the carbohydrate analogues 2 and 3 serve as precursors for biologically important compounds and several natural products.

  23. Short Communications

    1. Radical Polar Reactions

      Zinc Radical Transfer Based Modular Approach to Enantiopure Alkylidene-β-prol­ines from N-(tert-Butylsulfinyl)-α-(aminomethyl)acrylates

      Redouane Beniazza, Elise Romain, Fabrice Chemla, Franck Ferreira, Olivier Jackowski and Alejandro Perez-Luna

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501173

      Thumbnail image of graphical abstract

      N-(tert-Butylsulfinyl)-α-(aminomethyl)acrylates with tethered silylated alkynes undergo tandem 1,4-addition/carbozincation upon exposure to dialkylzinc compounds in the presence of air. High levels of chiral induction from the tert-butylsulfinyl directing group are achieved by adding samarium(III) triflate [Sm(OTf)3]; the reaction provides modular access to enantiopure (E)-4-alkylidene β-prolines.

    2. Helical Structures

      Synthesis and Structure of N-Hetero-ortho-phenylene Hexamers Containing 2,3-Substituted Pyridine Moieties

      Yuichiro Tokoro, Nobuhiko Ohtsuka, Ayumi Toh and Shin-ichi Fukuzawa

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501270

      Thumbnail image of graphical abstract

      Two pyridine rings are substituted for benzene rings in ortho-phenylene hexamers, which are stacked in a helical conformation. Directive stacking of pyridine rings effectively stabilizes a 3:1 helical conformation, as compared with other possible conformers, even in CDCl3.

    3. Natural Products

      The Revised Structure of Trichodermatide A

      Hiroki Shigehisa, Harue Kikuchi, Tsuyoshi Suzuki and Kou Hiroya

      Article first published online: 9 NOV 2015 | DOI: 10.1002/ejoc.201501281

      Thumbnail image of graphical abstract

      A revised structure for trichodermatide A is proposed. The revision is supported by the X-ray structure of a synthetic intermediate synthesized according to our previous route for trichodermatide A. The revised stereochemistry was also supported by NOESY experiment. Finally, we synthesized Trauner's compound corresponding to the originally reported structure from our synthetic intermediate of trichodermatide A through a Mitsunobu reaction at C10.

  24. Full Papers

    1. Polycyclic Aromatics

      Regioselective Annulation of Unsymmetrical 1,2-Phenylenebis(diaryl/diheteroarylmethanol): A Facile Synthesis of Anthracene, Tetracene, and Naphtho[b]thiophene Analogues

      Ramakrishnan Sivasakthikumaran, Settu Muhammad Rafiq, Elumalai Sankar, J. Arul Clement and Arasambattu K. Mohanakrishnan

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501087

      Thumbnail image of graphical abstract

      Regioselective cyclization of benzene- and naphthalene-based unsymmetrical diols with HBr (33 %) in acetic acid at room temperature led to the formation of annulated arenes and heteroarenes in good to excellent yields.

    2. C–H Arylation

      Cu/Pd-Catalyzed C-2–H Arylation of ­Quinazolin-4(3H)-ones with (Hetero)aryl Halides

      Julien Godeau, Marine Harari, Sylvain Laclef, Emmanuel Deau, Corinne Fruit and Thierry Besson

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501129

      Thumbnail image of graphical abstract

      The regiospecific C-2–H arylation of N-3-substituted quinazolin-4(3H)-ones with a wide range of aryl or (hetero)aryl halides under microwave irradiation is studied.

    3. Angularly Fused Furans

      DABCO-Promoted One-Pot Facile Synthesis of Angularly Fused Furoquinol­inones and Furocoumarins

      Monoranjan Ghosh and Alakananda Hajra

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501152

      Thumbnail image of graphical abstract

      A method for the regioselective synthesis of angularly fused polysubstituted furan derivatives by a DABCO-promoted intermolecular cyclization between enols and nitrostyrenes was developed. The reaction has great advantages in terms of its operational simplicity, cost-effectiveness, and environmental impact.

    4. [2+2+2] Cycloaddition Reaction

      An Eco-Friendly Route to N-Arylindoles by Iron-Catalyzed [2+2+2] Cycloaddition of Diynes with (Indol-1-yl)alkynes

      Hrishikesh Chowdhury, Nachiketa Chatterjee and Avijit Goswami

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501166

      Thumbnail image of graphical abstract

      A new method for the synthesis of N-arylindoles by using a [2+2+2] cycloaddition reaction between diynes and indole-N-alkynes has been established. This protocol employs FeCl2·4H2O/2-[(2,6-diisopropylphenyl)iminomethyl]pyridine (dipimp)/Zn as the catalyst system and ethanol as the solvent and provides easy access to indole-N-substituted fused arenes under green reaction conditions.

    5. Stereoselective Reduction

      Facile and Highly Diastereoselective Synthesis of syn- and cis-1,2-Diol Derivatives from Protected α-Hydroxy Ketones

      Emanuela Jahn, Jakub Smrček, Radek Pohl, Ivana Císařová, Peter G. Jones and Ullrich Jahn

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501174

      Thumbnail image of graphical abstract

      Monoprotected syn- and cis-1,2-diols were synthesized by reduction of ketones bearing the stereodirecting α-(2,2,6,6-tetramethylpiperidinyloxy) group. The latter induces syn- or cis-selectivity in unhindered acyclic or cyclic ketones with L-Selectride, whereas the smaller LiAlH4 induced excellent diastereoselectivity with hindered ketones. Free 1,2-diols were liberated by reductive N–O bond cleavage.

  25. Short Communications

    1. Chiral Arenes

      An Enantiopure 5,5′-Bitetracene

      Shinji Toyota, Ryutaro Miyaji, Yuta Yamamoto, Masataka Inoue, Kan Wakamatsu and Tetsuo Iwanaga

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501135

      Thumbnail image of graphical abstract

      5,5′-Bitetracene derivatives were synthesized and enantiomerically resolved by chiral HPLC as novel biaryl derivatives. The absolute stereochemistry was determined by the CD spectra, which showed characteristic coupled bands around 290 nm due to the exciton coupling of the two tetracene chromophores.

    2. Indene Synthesis

      Iodine-Catalyzed Synthesis of Highly Functionalized 1H-Indene Derivatives from Michael Adducts of o-Alkynylarene Chalcones with Diethyl Malonate

      Sikkandarkani Akbar and Kannupal Srinivasan

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501141

      Thumbnail image of graphical abstract

      The Michael adducts of o-alkynylarene chalcones with diethyl malonate undergo a Conia-ene reaction upon treatment with iodine to yield 1H-indene derivatives.

    3. Photoredox Catalysis

      Visible-Light, Metal-Free α-Amino C(sp3)–H Activation through 1,5-Hydrogen Migration: A Concise Method for the Preparation of Bis(indolyl)alkanes

      Saad Shaaban, Alexander Roller and Nuno Maulide

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501149

      Thumbnail image of graphical abstract

      A photoredox catalytic, metal-free method for C–H functionalization α to amines is developed. This transformation directly affords bis(indolyl)alkane products in good to excellent yields. The process hinges on a pivotal 1,5-H migration to an aryl radical intermediate, which ultimately leads to a reactive azacarbenium ion.

  26. Full Papers

    1. Rare Nitro Compounds

      Reinvestigation of the Nitration of Tri­chloroethene – Subsequent Reactions of the Products and Evaluation of Their Anti­microbial and Antifungal Activity

      Viktor A. Zapol'skii, Jan C. Namyslo, Galina Sergeev, Mark Brönstrup, Mimoza Gjikaj and Dieter E. Kaufmann

      Article first published online: 6 NOV 2015 | DOI: 10.1002/ejoc.201501066

      Thumbnail image of graphical abstract

      Trichloronitroethene and 1,2,2-trichloro-2-nitroethyl [chloro(nitro)methylene]azinate, nitration products of trichloroethene, are buildings blocks for O-(1,2,2-trichloro-2-nitroethyl) oximes, 1,1-diamino-2-chloro-2-nitroethenes, 2-nitroethoxyguanidines, and carbimidoyl halides. Some compounds show high activity against Staphylococcus aureus and reduce the viability of the MCF-7 cancer cell lines.

    2. Stereoselective Reactions

      Reactivity of α-Bromosulfones Obtained from gem-Dibromides

      Niels Münster, Laura Werel, Georg Alexander Rennar, Klaus Harms and Ulrich Koert

      Article first published online: 3 NOV 2015 | DOI: 10.1002/ejoc.201501136

      Thumbnail image of graphical abstract

      The SN2 reaction of β-hydroxy-gem dibromides with aromatic sulfinates gives α-bromo-sulfones diastereoselectively. Lithiation and subsequent alkylation at –78 °C in Et2O proceeds by equilibration of the configurationally unstable organolithium intermediate. Reaction of α-bromosulfones with methyl cuprate results in substitution of the bromine atom.

    3. Multicomponent Domino Reactions

      Rapid Access to Polyfunctionalized 3,4-Dihydroquinazolinones through a Sequential N-Acyliminium Ion Mannich Reaction Cascade

      Rajiv T. Sawant, Marc Y. Stevens and Luke R. Odell

      Article first published online: 3 NOV 2015 | DOI: 10.1002/ejoc.201501178

      Thumbnail image of graphical abstract

      A microwave-promoted one-pot, three-component sequential cyclization–Mannich reaction of unactivated ketones, o-formyl carbamates, and primary amines has been developed. Cyclic N-acyliminium ions are generated in situ during the course of this metal-free protocol, which provides rapid access to structurally diverse 3,4-dihydroquinazolinones in good to excellent yields with high regioselectivity.

    4. Alkylation Using Alcohols

      Pd/C-Catalyzed Alkylation of Heterocyclic Nucleophiles with Alcohols through the “Borrowing Hydrogen” Process

      Anggi Eka Putra, Yohei Oe and Tetsuo Ohta

      Article first published online: 3 NOV 2015 | DOI: 10.1002/ejoc.201501030

      Thumbnail image of graphical abstract

      Pd/C was found to be an effective catalyst for the alkylation of heterocyclic compounds using alcohols as the alkylating agents. The catalyst can be recovered and reused with a turnover number (TON) of up to 900. Moreover, the reaction is scalable.

  27. Microreviews

    1. Anti-Ebola Virus Agents

      Small-Molecule Therapeutics for Ebola Virus (EBOV) Disease Treatment

      Kunisuke Izawa, José Luis Aceña, Jiang Wang, Vadim A. Soloshonok and Hong Liu

      Article first published online: 3 NOV 2015 | DOI: 10.1002/ejoc.201501158

      Thumbnail image of graphical abstract

      This review highlights the discovery, synthesis, and modes of action of three antiviral compounds currently in development against Ebola virus (EBOV) infection.

  28. Full Papers

    1. Radical Thiol Addition

      Conjugation of Bioactive Molecules to a Fluorescent Dithiomaleimide by Photoin­duced and BEt3-Initiated Thio-Click Reactions

      László Lázár, Miklós Nagy, Anikó Borbás, Pál Herczegh, Miklós Zsuga and Sándor Kéki

      Article first published online: 22 OCT 2015 | DOI: 10.1002/ejoc.201501116

      Thumbnail image of graphical abstract

      Thio-click chemistry and maleimide chemistry were combined, for the first time, to couple fluorescent dithiomaleimide to biologically active compounds. Of the two activation methods tested, Et3B-initiated hydrothiolation was superior to photoinduced variants. All of the hydrothiolation products showed green fluorescence with relatively high quantum yields.


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